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Book Details
Abstract
Containing the very latest information on all aspects of enthalpy and internal energy as related to fluids, this book brings all the information into one authoritative survey in this well-defined field of chemical thermodynamics. Written by acknowledged experts in their respective fields, each of the 26 chapters covers theory, experimental methods and techniques and results for all types of liquids and vapours. These properties are important in all branches of pure and applied thermodynamics and this vital source is an important contribution to the subject hopefully also providing key pointers for cross-fertilization between sub-areas.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Copyright | iv | ||
| Foreword | v | ||
| Preface | vii | ||
| References | x | ||
| Contents | xi | ||
| Chapter 1 Internal Energy and Enthalpy: Introduction, Concepts and Selected Applications | 1 | ||
| 1.1 Introduction | 1 | ||
| 1.2 Thermodynamic Fundamentals | 3 | ||
| 1.3 More Thermodynamics and Selected Applications | 14 | ||
| 1.3.1 Properties of Real Fluids | 14 | ||
| 1.3.2 Property Changes of Mixing | 41 | ||
| 1.4 Concluding Remarks, Outlook and Acknowledgements | 51 | ||
| References | 53 | ||
| Chapter 2 Macroscopic Energy and Entropy Balances in Phase Equilibrium Studies | 62 | ||
| 2.1 Introduction | 62 | ||
| 2.2 Derivation of Macroscopic Balances | 63 | ||
| 2.3 Equations | 63 | ||
| 2.3.1 Macroscopic Energy Balance | 63 | ||
| 2.3.2 Macroscopic Mechanical Energy Balance | 64 | ||
| 2.3.3 Macroscopic Entropy Balance | 64 | ||
| 2.4 Application of Macroscopic Balances | 64 | ||
| 2.4.1 Differential Ebulliometry | 64 | ||
| 2.5 Macroscopic Balances in Flow Calorimetry | 71 | ||
| 2.6 Some Useful Derivative Relations | 73 | ||
| 2.6.1 Limiting Activity Coefficients | 73 | ||
| 2.6.2 Temperature and Pressure Derivatives | 74 | ||
| References | 76 | ||
| Chapter 3 Enthalpy Measurements of Condensed Matter by Peltier-element-based Adiabatic Scanning Calorimetry (pASC) | 77 | ||
| 3.1 Introduction | 77 | ||
| 3.2 Operational Principle of Adiabatic Scanning Calorimetry | 78 | ||
| 3.3 Peltier-element-based Adiabatic Scanning Calorimeter (pASC) | 79 | ||
| 3.4 Comparison with DSC | 82 | ||
| 3.5 The pASC as Adiabatic Heat-step Calorimeter | 83 | ||
| 3.6 The pASC as Heat-flux DSC-type Constant-rate Calorimeter | 84 | ||
| 3.7 The pASC as Power-compensated DSC-type Constant-rate Calorimeter | 84 | ||
| 3.8 High-resolution pASC Data near the Melting Point of Gallium | 85 | ||
| 3.8.1 pASC Constant Power Scanning Results | 85 | ||
| 3.8.2 pASC Heat-step Results | 86 | ||
| 3.8.3 pASC Heat-flux and Power-compensated DSC-type Scanning Results | 87 | ||
| 3.9 High-resolution pASC Data near Phase Transitions in Lipid Vesicles | 89 | ||
| 3.10 High-resolution pASC Data for the Melting of Water | 89 | ||
| 3.11 High-resolution pASC Data for Phase Transitions in a Liquid Crystal | 92 | ||
| References | 94 | ||
| Chapter 4 Isothermal Titration Calorimetry | 96 | ||
| 4.1 Introduction | 96 | ||
| 4.2 Thermodynamic Models of the Titration Processes in Isothermal Titration Calorimetry | 102 | ||
| 4.2.1 The Process of Titration in the Different Types of Titration Cells | 102 | ||
| 4.2.1.1 Titration Process in Open Titration Cells | 103 | ||
| 4.2.1.2 Titration Process in Full Titration Cells | 107 | ||
| 4.2.2 Run Types in Isothermal Titration Calorimetry | 107 | ||
| 4.2.2.1 Concentration Run | 108 | ||
| 4.2.2.2 Dilution Run | 109 | ||
| 4.2.2.3 Concentration-dilution Run | 110 | ||
| 4.2.3 Finite Titrations | 112 | ||
| 4.2.3.1 Finite Titrations in Open Titration Cells | 113 | ||
| 4.2.3.2 Finite Titrations in Full Titration Cells | 114 | ||
| 4.2.4 Infinitesimal Titrations | 116 | ||
| 4.2.4.1 Definitions and Properties of the Infinitesimal Titration | 116 | ||
| 4.2.4.2 Thermodynamic Equations of the Infinitesimal Titrations Along Different Runs | 119 | ||
| 4.3 Interaction of Solutes in Dilute Solutions by Isothermal Titration Calorimetry | 121 | ||
| 4.3.1 Study of the Single Ligand Binding Site Model | 122 | ||
| Acknowledgments | 129 | ||
| References | 129 | ||
| Chapter 5 Calorimetric Determination of Enthalpies of Vaporization | 133 | ||
| 5.1 Introduction | 133 | ||
| 5.2 Theoretical Considerations | 134 | ||
| 5.3 Calorimetric Determination of the Enthalpy of Vaporization | 136 | ||
| 5.3.1 Condensation Apparatuses | 137 | ||
| 5.3.1.1 Condensation Calorimeters | 137 | ||
| 5.3.1.2 Reference Liquid Boil-off Calorimeter | 139 | ||
| 5.3.2 Vaporization Calorimetry | 141 | ||
| 5.3.2.1 Moderate and High Vapor Pressures | 142 | ||
| 5.3.2.1.1 Recycle Flow Method | 142 | ||
| 5.3.2.1.2 Method of Controlled Withdrawal of Vapor Phase | 144 | ||
| 5.3.2.2 Low Pressures | 147 | ||
| 5.3.2.2.1 Vaporization to a Gas Stream | 147 | ||
| 5.3.2.2.2 Vaporization into Vacuum | 151 | ||
| 5.3.3 Differential Scanning Calorimetry | 154 | ||
| 5.3.4 Fast Scanning Calorimeter (FSC) | 155 | ||
| 5.4 Conclusions | 156 | ||
| References | 156 | ||
| Chapter 6 Energetic Effects in Hydrogen-bonded Liquids and Solutions | 159 | ||
| 6.1 Introduction | 159 | ||
| 6.2 Pure Associated Liquids | 162 | ||
| 6.2.1 Partitioning of the Heat Capacity of Liquids | 162 | ||
| 6.2.2 Two-state Association Model | 163 | ||
| 6.3 Nonaqueous Associated Solutions | 165 | ||
| 6.3.1 Two-state Behaviour for the Excess Heat Capacity | 165 | ||
| 6.3.2 Inert Solvents versus Proton Acceptors | 166 | ||
| 6.4 Cold Water | 168 | ||
| 6.4.1 Anomalous Thermodynamics | 168 | ||
| 6.4.2 Two-state Analysis | 169 | ||
| 6.5 Hydrophobicity | 170 | ||
| 6.5.1 Hydration Phenomena | 170 | ||
| 6.5.2 Aggregation of Small Amphiphiles | 171 | ||
| 6.6 Final Remarks | 174 | ||
| Acknowledgments | 175 | ||
| References | 175 | ||
| Chapter 7 Thermodynamic Studies of Inclusion Compounds of Cyclodextrin | 179 | ||
| 7.1 Introduction | 179 | ||
| 7.2 Methods of Determination | 180 | ||
| 7.2.1 Experimental | 180 | ||
| 7.2.2 Theoretical | 181 | ||
| 7.2.3 Quantum Chemical Approach | 183 | ||
| 7.3 Thermodynamic Parameters | 183 | ||
| 7.3.1 Enthalpy of Dilution | 183 | ||
| 7.3.2 Effect of Aliphatic Group Size on α-CD Inclusion Compounds | 184 | ||
| 7.3.2.1 α-CD+Aliphatic Alcohols | 184 | ||
| 7.3.2.2 α-CD+Diols | 189 | ||
| 7.3.2.3 α-CD+Aliphatic Nitrils | 190 | ||
| 7.3.2.4 Difference Between Inclusion Compounds of Aliphatic Alcohols and Nitriles with α-CD | 194 | ||
| 7.3.3 Positional Effect of Hydroxyl Groups in Butanediol Isomers | 196 | ||
| 7.3.3.1 Inclusion of Butanediols into α-CD | 196 | ||
| 7.3.3.2 Inclusion of Butanol Isomers into α-CD | 196 | ||
| 7.3.4 Effect of Guest Molecule Functional Groups on Inclusion into α-CD | 199 | ||
| 7.3.4.1 α-CD+Propane Derivatives | 199 | ||
| 7.3.4.2 α-CD+Butane Derivatives | 200 | ||
| 7.3.4.3 α-CD+Pentane Derivatives | 200 | ||
| 7.3.4.4 Inclusion of Propane, Butane, and Pentane Derivatives into α-CD | 200 | ||
| 7.4 Discussion | 202 | ||
| 7.4.1 Entropy-Enthalpy Compensation | 205 | ||
| 7.5 Closing Remarks | 206 | ||
| References | 206 | ||
| Chapter 8 Thermodynamic Studies of Chiral Compounds | 212 | ||
| 8.1 Introduction | 212 | ||
| 8.2 Material and Method | 214 | ||
| 8.2.1 Material | 214 | ||
| 8.2.2 Calorimetry | 214 | ||
| 8.2.3 Theoretical Application | 215 | ||
| 8.3 Enthalpic Behaviour | 217 | ||
| 8.3.1 Enthalpies of Mixing for Pure Enantiomers in the Liquid State | 217 | ||
| 8.3.1.1 Interaction of Enantiomers with Large Hydrophobic Groups | 218 | ||
| 8.3.1.2 Correlation Between the Cohesive Energy Densities and the Enthalpies of Mixing\r | 220 | ||
| 8.3.1.3 Molecular Interaction of Chiral Molecules | 222 | ||
| 8.3.2 Interaction of Enantiomers in the Solution State | 222 | ||
| 8.3.2.1 Solid Enantiomers in Solution | 223 | ||
| 8.3.2.1.1 Enantiomers of Camphor and its Derivatives in Solution | 223 | ||
| 8.3.2.1.2 Enantiomers of Dicarboxylic Acids in Solution | 225 | ||
| 8.3.2.2 Liquid Enantiomers in Solution | 227 | ||
| 8.3.2.2.1 Enantiomers of Limonene in Solution | 227 | ||
| 8.3.2.2.2 Enantiomers of Fenchone in Solution | 235 | ||
| 8.4 Theoretical Comparison | 237 | ||
| 8.4.1 Solution Theory: Intermolecular Interaction of Enantiomers | 239 | ||
| 8.4.2 Quantum Chemical Calculation | 241 | ||
| 8.4.3 Molecular Dynamics Calculation | 242 | ||
| 8.5 Closing Remarks | 243 | ||
| References | 243 | ||
| Chapter 9 Temperature Dependence of the Enthalpy of Alkanes and Related Phase Change Materials (PCMs) | 246 | ||
| 9.1 Introduction | 246 | ||
| 9.2 Experimental Details | 248 | ||
| 9.3 Pure Alkanes and Rotator Phases | 248 | ||
| 9.3.1 Background | 248 | ||
| 9.3.2 Phase Transitions | 250 | ||
| 9.3.3 Overview | 251 | ||
| 9.3.4 RI-RII Transition | 252 | ||
| 9.3.5 RV-RI Transition | 255 | ||
| 9.3.6 Other Transitions | 255 | ||
| 9.4 PCMs and Stored Heat | 256 | ||
| 9.4.1 Background | 256 | ||
| 9.4.2 PCMs | 257 | ||
| 9.4.3 Alkane Mixtures | 258 | ||
| 9.4.4 Fatty Acids | 259 | ||
| 9.4.5 Water and Water-Salt Eutectics | 259 | ||
| 9.4.6 Composites and Encapsulation | 260 | ||
| 9.4.6.1 Overview | 261 | ||
| 9.4.6.2 Cooling | 262 | ||
| 9.4.6.3 Transition Heat and Storage Capacity | 263 | ||
| 9.4.6.4 Rotator Phases | 264 | ||
| 9.5 Summary and Conclusion | 266 | ||
| References | 266 | ||
| Chapter 10 Enthalpy Changes on Solution of Gases in Liquids | 269 | ||
| 10.1 Introduction | 269 | ||
| 10.2 Thermodynamics | 270 | ||
| 10.2.1 Gas Solubility | 270 | ||
| 10.2.2 Calorimetry | 281 | ||
| 10.3 Selected Results | 291 | ||
| 10.4 Concluding Remarks | 293 | ||
| References | 294 | ||
| Chapter 11 Titration Calorimetry and Differential Scanning Calorimetry of Lipid-Protein Interactions | 299 | ||
| 11.1 Introduction | 299 | ||
| 11.2 Isothermal Titration Calorimetry | 300 | ||
| 11.2.1 Binding of Apolipoprotein A-1 (Apo A-1) to Lipid Vesicles | 300 | ||
| 11.2.2 Langmuir Multi-site Binding Isotherm | 303 | ||
| 11.2.3 LAH4-L1-into-lipid Isothermal Titration Calorimetry | 304 | ||
| 11.2.4 Surface Partition Equilibrium and Gouy-Chapman Theory | 306 | ||
| 11.3 Differential Scanning Calorimetry of Lipid-Protein Interactions | 308 | ||
| 11.3.1 Thermal Unfolding of Apo A-1 in Solution and in Membranes | 308 | ||
| 11.3.2 The 2-state Model Applied to Apo A-1 | 310 | ||
| 11.3.3 Zimm-Bragg Theory | 311 | ||
| Chapter 12 Biocalorimetry: Differential Scanning Calorimetry of Protein Solutions | 315 | ||
| 12.1 Introduction | 315 | ||
| 12.2 The Two-state Unfolding Model for Monomeric Proteins | 318 | ||
| 12.3 The Three-state and Multi-state Unfolding Models for Monomeric Proteins | 321 | ||
| 12.4 The Study of Protein-ligand and Protein-Protein Interactions by DSC | 322 | ||
| 12.5 DSC Analysis of Protein Oligomers and Aggregates | 325 | ||
| 12.6 Non-equilibrium Transitions | 328 | ||
| 12.7 Conclusions | 331 | ||
| References | 331 | ||
| Chapter 13 Biocalorimetry of Plants, Insects and Soil Microorganisms | 336 | ||
| 13.1 Introduction | 336 | ||
| 13.2 Biocalorimetry of Plants | 340 | ||
| 13.3 Biocalorimetry of Insects | 345 | ||
| 13.3.1 Cold Hardiness | 350 | ||
| 13.3.2 Whole Body Supercooling Points | 350 | ||
| 13.3.3 Assessment of Pesticide Activity | 351 | ||
| 13.3.4 Development of Postharvest Quarantine Treatments | 351 | ||
| 13.4 Biocalorimetry of Soil Organic Matter | 353 | ||
| References | 358 | ||
| Chapter 14 Temperature Dependence of the Enthalpy Near Critical and Tricritical Second-order and Weakly First-order Phase Transitions | 364 | ||
| 14.1 Introduction | 364 | ||
| 14.2 Temperature Dependence of the Enthalpy at the Liquid-Liquid Critical Point | 366 | ||
| 14.3 Enthalpy Temperature Dependence at Weakly First-order and Tricritical Second-order Phase Transitions | 369 | ||
| 14.3.1 Enthalpy Temperature Dependence at the Weakly First-order Isotropic to Nematic Transition | 370 | ||
| 14.3.2 Enthalpy Temperature Dependence at the Nematic to Smectic A Phase Transition | 371 | ||
| References | 378 | ||
| Chapter 15 Yang–Yang Critical Anomaly | 380 | ||
| 15.1 Background | 380 | ||
| 15.2 Isochoric Heat Capacity and Liquid-Gas Asymmetry | 384 | ||
| 15.3 Yang-Yang Critical Anomaly Strength and Distinct Two-phase Isochoric Heat Capacity Contributions near the Liquid-Gas Critical Point | 392 | ||
| 15.4 New Method for Evaluation of the Yang-Yang Anomaly Parameter from Direct Measurements of Two-phase Isochoric Heat Capacity and Saturated Liquid and Vapor Density | 397 | ||
| 15.5 Conclusions | 405 | ||
| Acknowledgments | 406 | ||
| References | 406 | ||
| Chapter 16 Internal Pressure and Internal Energy of Saturated and Compressed Phases | 411 | ||
| 16.1 Background | 411 | ||
| 16.2 Thermodynamic and Statistical Mechanical Definition of the Internal Pressure | 412 | ||
| 16.3 Internal Pressure and Intermolecular Forces | 414 | ||
| 16.4 Methods for Internal Pressure Measurements | 418 | ||
| 16.5 One-phase Isochoric Heat Capacity and Internal Pressure | 423 | ||
| 16.6 Two-phase Isochoric Heat Capacity and Internal Pressure | 427 | ||
| 16.7 Internal Pressure as a Function of External Pressure, Temperature or Density from a Reference Equation of State | 434 | ||
| 16.8 Locus of Zero Internal Pressure | 438 | ||
| 16.9 Simon's Melting Curve Equation Parameters and Internal Pressure | 439 | ||
| Acknowledgments | 442 | ||
| References | 442 | ||
| Chapter 17 Solubility Parameters: A Brief Review | 447 | ||
| 17.1 Introduction and Development of Concept | 447 | ||
| 17.2 Expanded Regular Solution Theory | 456 | ||
| 17.3 Effect of Temperature and Pressure on Solubility Parameters | 459 | ||
| 17.4 Empiricism and Further Developments, and Concluding Remarks | 463 | ||
| References | 470 | ||
| Chapter 18 Internal Pressure of Liquids: A Review | 477 | ||
| 18.1 Introduction | 477 | ||
| 18.2 Internal Pressures of Neat Liquids | 479 | ||
| 18.2.1 Liquefied Gases | 479 | ||
| 18.2.2 Liquid Metallic Elements | 480 | ||
| 18.2.3 Molecular Liquids at Ambient Conditions | 480 | ||
| 18.2.4 Liquid Polymers | 481 | ||
| 18.2.5 Room Temperature Ionic Liquids (RTILs) | 481 | ||
| 18.2.6 Molten Salts | 483 | ||
| 18.2.7 Internal Pressure Dependence on the Temperature and Pressure | 485 | ||
| 18.2.8 Correlations with Other Quantities | 491 | ||
| 18.2.9 Internal Pressure of Solvents and Reactions in Them | 492 | ||
| 18.3 Internal Pressure of Liquid Mixtures and Solutions | 493 | ||
| 18.3.1 Liquid Mixtures | 493 | ||
| 18.3.2 Dilute Solutions of Non-electrolytes | 495 | ||
| 18.3.3 Dilute Solutions of Electrolytes | 497 | ||
| 18.4 Discussion and Conclusions | 500 | ||
| References | 501 | ||
| Chapter 19 Excess Enthalpies for Binary Systems Containing Ionic Liquids | 505 | ||
| 19.1 Introduction | 505 | ||
| 19.2 Experimental Methodologies | 506 | ||
| 19.3 Results and Discussion | 506 | ||
| 19.3.1 Aqueous Systems | 507 | ||
| 19.3.2 Alcohol Systems | 511 | ||
| 19.3.3 Other Systems | 516 | ||
| 19.4 Conclusions | 518 | ||
| References | 518 | ||
| Chapter 20 Electrolyte Solutions: Standard State Partial Molar Enthalpies of Aqueous Solution up to High Temperatures | 521 | ||
| 20.1 Introduction | 521 | ||
| 20.2 Experimental Methods | 523 | ||
| 20.2.1 The Integral Heat Method | 524 | ||
| 20.2.2 Treatment of Data | 525 | ||
| 20.2.3 Differential Heat Capacity Calorimeters | 534 | ||
| 20.2.4 Other Methods | 537 | ||
| 20.3 Conclusion | 538 | ||
| References | 538 | ||
| Chapter 21 Correlation and Prediction of Excess Molar Enthalpies Using DISQUAC | 543 | ||
| 21.1 Introduction | 543 | ||
| 21.2 Main Hypotheses and Equations | 545 | ||
| 21.2.1 Hypotheses | 545 | ||
| 21.2.2 Equations | 546 | ||
| 21.3 Fitting the Interaction Parameters | 548 | ||
| 21.4 Interaction Parameters and Molecular Structure | 549 | ||
| 21.5 Selected Data | 551 | ||
| 21.6 Results | 551 | ||
| 21.6.1 Group I | 552 | ||
| 21.6.2 Group II | 554 | ||
| 21.6.3 Group III | 556 | ||
| 21.6.4 Group IV | 557 | ||
| 21.6.5 Group V | 560 | ||
| 21.6.6 Ternary Mixtures | 562 | ||
| 21.7 Concluding Remarks | 562 | ||
| References | 563 | ||
| Chapter 22 Molecular Thermodynamics of Solutions | 569 | ||
| 22.1 Introduction | 569 | ||
| 22.2 The Non-random Hydrogen-bonding Model | 570 | ||
| 22.2.1 The Essentials of the Model | 570 | ||
| 22.2.2 The Hydrogen Bonding Contribution | 573 | ||
| 22.2.3 The Dimerization of Acids | 574 | ||
| 22.2.4 Intra-molecular Hydrogen Bonding | 575 | ||
| 22.3 Applications | 576 | ||
| 22.3.1 Systems with Carboxylic Acids | 577 | ||
| 22.3.2 Systems with Intra-molecular Association | 585 | ||
| 22.4 Conclusions | 587 | ||
| References | 587 | ||
| Chapter 23 Measurement of Heat Capacity and Phase Transition Enthalpy for Condensed Materials by Precision Adiabatic Calorimetry | 590 | ||
| 23.1 Introduction | 590 | ||
| 23.2 A New Adiabatic Calorimeter | 592 | ||
| 23.2.1 Sample Cell and Adiabatic Calorimetric Cryostat | 593 | ||
| 23.2.2 Computer, Data Collection Unit and Software | 594 | ||
| 23.2.3 Adiabatic Control Module | 599 | ||
| 23.2.4 The Module of Setting and Revision of Operation Conditions and Data Displaying | 599 | ||
| 23.2.5 Calibration and Discussion of Results | 599 | ||
| 23.3 Application of the Adiabatic Calorimeter in Measurement of Heat Capacity and Phase Transition Enthalpy of Ionic Liquids | 601 | ||
| 23.3.1 Material, Adiabatic Calorimetry and TG Analysis | 601 | ||
| 23.3.2 Heat Capacity | 602 | ||
| 23.3.3 The Temperature, Enthalpy and Entropy of Solid-Liquid Phase Transition | 605 | ||
| 23.3.4 Thermodynamic Functions of the Compound | 606 | ||
| 23.3.5 The Results of TG-DTG Analysis | 606 | ||
| 23.4 Conclusions | 607 | ||
| Acknowledgments | 608 | ||
| References | 608 | ||
| Subject Index | 611 |